JPH0931316A - Copolycarbonate composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a copolycarbonate composition having excellent moldability and giving a molding improved in appearance such as hue stability and surface gloss by mixing a copolycarbonate comprising at least two kinds of specified structural units with a filler. SOLUTION: This copolycarbonate composition is obtained by adding 2-95 pts.wt. filler to 98-5 pts.wt. copolycarbonate obtained by melt-polycondensing 1mol of a mixture of 1mol of an aromatic dihydroxy compound which gives a structural unit of formula I [wherein X is (R<3> -)C(-R<4> -), C(=R<5> ) or the like; R<3> and R<4> are each H, a monovalent hydrocarbon group or the like; R<5> is a bivalent hydrocarbon group or the like; R<1> s are the same or mutually different 1-10C hydrocarbon groups or the like; R<2> s are the same as R<1> s; and (m) and (n) are each 0-4] and 8×10<5> -3×10<-2> mol of an aromatic dihydroxy compound of formula II[ wherein Y is (R<3> '-)-(-R<4> '), C(=R<5> ') or the like; R<7> s are the same or mutually different 1-10C hydrocarbon groups or the like; R<8> s are the same as R<7> s; (p) is 0-4; and (q) is 0-3] with 1.0-1.30mol of a carbonic diester in the presence of 10<-8> -10<-3> mol of a catalyst selected from among alkali and alkaline earth metal compounds.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to copolycarbonate compositions, and more particularly to such compositions containing branched copolycarbonates.

[0002]

Polycarbonate is
It is widely used because it has excellent mechanical properties such as impact resistance, heat resistance, and transparency.

A generally known polycarbonate is produced by using bisphenol A as a dihydroxy component and has a linear molecular structure having a bisphenol A skeleton.

However, a polycarbonate having such a linear molecular structure may be inferior in melt elasticity and melt strength during melt molding, and improvement in molding characteristics such as melt elasticity and melt strength is desired. As a method of improving such molding characteristics, a method of copolymerizing a polyfunctional compound to branch a polycarbonate is generally known (JP-A-4-89824).

The inventors of the present invention have already disclosed in JP-A-7-149887 that a novel branched polymer having excellent molding properties such as melt elasticity and melt strength, as well as excellent heat resistance, water resistance and hue stability. A copolycarbonate was provided.

On the other hand, in the conventional homopolycarbonate having a bisphenol A skeleton, when a filler such as glass fiber is added, there is a problem that the fluidity is lowered and the appearance such as surface gloss is impaired.

An object of the present invention is to provide a copolycarbonate composition which is excellent in moldability and has a good appearance such as hue stability and surface gloss of a molded product.

[0008]

SUMMARY OF THE INVENTION The inventors have found that a composition comprising a specific copolycarbonate having a branch and a filler can overcome the above-mentioned problems in the conventional polycarbonate / filler composition. The present invention has been completed.

That is, the present invention is a copolycarbonate obtained by copolymerizing (A) two or more kinds of aromatic dihydroxy compounds and a compound capable of introducing a carbonic acid bond, which is derived from the aromatic dihydroxy compound. As a component unit, the following formula [I]:

[0010]

Embedded image (In the formula, X is ^{- (R 3 -) C (} -R 4) -, - C
^{(= R 5) -, -} O -, - S -, - SO- or -SO
_2- {wherein R ³ and R ⁴ are a hydrogen atom or a monovalent hydrocarbon group optionally substituted with halogen, and R ⁵
Is a divalent hydrocarbon group that may be substituted with halogen}, and R ¹ and R ² may be the same or different, and the number of carbon atoms that may be substituted with halogen, respectively. 1 to 10 hydrocarbon groups or halogen atoms, m and n represent the number of substituents, each independently an integer of 0 to 4), and the following formula [II]:

[0011]

Embedded image (In the above formula, Y is-(R3 ^' -) C (-R4 ^' )-, -C
(= R5 ^' )-, -O-, -S-, -SO- or -SO
_2- {wherein R ^{3 '} and R ^4' are a hydrogen atom or a monovalent hydrocarbon group optionally substituted with halogen, and R ^{5 '}
Is a divalent hydrocarbon group which may be substituted with halogen}, and R ⁷ and R ⁸ may be the same or different and each has the number of carbon atoms which may be substituted with halogen. 1 to 10 hydrocarbon groups or halogen atoms, p and q represent the number of substituents, p is an integer of 0 to 4, and q is an integer of 0 to 3). A copolycarbonate composition comprising a copolycarbonate and (B) a filler.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First, the (A) copolycarbonate used in the present invention will be described. Particularly preferably,
In the above copolycarbonate, as a component unit derived from an aromatic dihydroxy compound, the above formula [I]
And the structural unit represented by the above formula [II], relative to 1 mol of the structural unit represented by [I],
The structural unit represented by [II] is contained at a ratio of 8 × 10 ^{−5 to} 3 × 10 ⁻² mol, and (2) in methylene chloride at 20 ° C.
Intrinsic viscosity [η] measured in 0.2-1.2 dl / g
It is.

Preferably, however, in the above formula [I], X
It is ^{- (R 3 -) C (} -R 4) -, - C (= R 5) -, -
O -, - S -, - SO- or -SO ₂ - {wherein R ³
And R ⁴ is a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms which may be substituted with halogen, and R ⁵ may be substituted with halogen. A straight, branched or cyclic divalent hydrocarbon group having 1 to 15 carbon atoms, and R ¹ and R ^1
2 may be the same or different and each is a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with halogen, or a halogen atom, and m and n Is as defined above. In the formula [II], Y is-(R3 ^' -) C (-R4 ^' )-, -C.
(= R5 ^' )-, -O-, -S-, -SO- or -SO
_2- {wherein R ^{3 ′} and R ^{4 ′} are a hydrogen atom or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms, which may be substituted with halogen, ^{5 'is} a straight-chain 1 to 15 carbon atoms which may be substituted with a halogen, a divalent hydrocarbon group branched or cyclic}, R ⁷ and R ⁸ are independently identical or different And a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with halogen, or a halogen atom, and p and q have the same meanings as described above.

In the above formula [I], it is particularly preferable that X is a straight chain or branched alkylene, and in the above formula [II], Y is a straight chain or branched alkylene.

The copolycarbonate (A) contains, as a constitutional unit derived from an aromatic dihydroxy compound, a constitutional unit represented by the above formula [I] and a constitutional unit represented by the above formula [II]. .

Among such aromatic dihydroxy compounds, examples of the aromatic dihydroxy compound for introducing the structural unit represented by the above formula [I] include, for example, the following formula [III]:

[0017]

Embedded image An aromatic dihydroxy compound represented by the formula (X, R ¹ , R ² , m and n have the same meanings as described above) can be used. Here, the monovalent hydrocarbon group includes a linear, branched or cyclic alkyl group, alkenyl group, aryl group (eg phenyl group), alkaryl group (eg toluyl group), aralkyl group (eg benzyl). Group) and the like. The monovalent hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms or an aryl group. Also,
Examples of the divalent hydrocarbon group include divalent groups in which these groups further have a free valence. Specific examples of such compounds include the following aromatic dihydroxy compounds: bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane,
2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) )
Bis (hydroxyaryl) alkanes such as propane and 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis ( Bis (hydroxyaryl) cycloalkanes such as 4-hydroxyphenyl) cyclohexane; 4,4'-dihydroxydiphenyl ether, dihydroxyaryl ethers such as 4,4'-dihydroxy-3,3'-dimethylphenyl ether; 4,4 Dihydroxydiaryl sulfides such as'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyl Dihydroxy diaryl sulfoxides such as diphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfone, 4,4'-di Such as dihydroxy diaryl sulfones such as Dorokishi 3,3'-dimethyl diphenyl sulfone.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

Next, as an aromatic dihydroxy compound for introducing the constitutional unit represented by the above formula [II], for example, general formula [IV]:

[0020]

[Chemical 6] (In the above formula, Y, R ⁷ , R ⁸ , p and q have the same meanings as described above, and R ⁶ is a hydrogen atom, a straight-chain, branched or C 1-20 optionally substituted halogen atom. An aromatic dihydroxy compound represented by a cyclic hydrocarbon group or a halogen atom) can be used. Specific examples of such a compound include the following aromatic dihydroxy compounds: 2- (4-hydroxyphenyl) -2- (3′-carboxy-4′-hydroxyphenyl) propane, 2- ( 4-hydroxyphenyl) -2- (3'-methoxycarbonyl-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3'-ethoxycarbonyl-4'-hydroxyphenyl) propane, 2 -(4-hydroxyphenyl) -2- (3'-butoxycarbonyl-4'-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) Methane, 2- (4-hydroxyphenyl)
-2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) ethane, 2- (4-hydroxyphenyl) -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) octane,
1- (4-hydroxyphenyl) -1- (3'-phenoxycarbonyl-4'-hydroxyphenyl) cyclopentane, 4-hydroxyphenyl-3'-phenoxycarbonyl-4'-hydroxyphenyl ether, 4-hydroxy Phenyl-3'-phenoxycarbonyl-4'-hydroxyphenyl sulfide, 4-
Hydroxyphenyl-3'-phenoxycarbonyl-4'-hydroxyphenyl sulfoxide, 4-hydroxyphenyl-
3'-phenoxycarbonyl-4'-hydroxyphenyl sulfone etc.

Among these, especially 2- (4-hydroxyphenyl) -2- (3'-carboxy-4'-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (3'-phenoxy Carbonyl-4'-hydroxyphenyl) propane is preferred.

Such compounds can be prepared by using the desired aromatic dihydroxy compound in Kolbe-Schmidt.
mitt) reaction by monocarboxylation,
Alternatively, it can be easily synthesized by further esterification.

In the (A) copolycarbonate,
It is preferable that the constitutional unit represented by [II] is contained at a ratio of 8 × 10 ^{−5 to} 3 × 10 ⁻² moles per 1 mole of the constitutional unit represented by [I], and more preferably 2.5. × 10 ^-4 ~
The ratio is 1 × 10 ⁻² mol, more preferably 5 × 10 ^{−4 to} 5 × 10 ⁻³ . If the amount of the structural unit represented by [II] is less than 8 × 10 ⁻⁵ mol, the melting property tends to deteriorate, and if it exceeds 3 × 10 ⁻² mol, the melt viscosity tends to be too high and the moldability tends to deteriorate.

The (A) copolycarbonate contains a carbonic acid bond, and such a carbonic acid bond can be introduced by using, for example, phosgene, carbonic acid diester or the like. Specific examples of the carbonic acid diester include the following compounds: diphenyl carbonate, ditolyl carbonate, and bis (chlorophenyl).
Carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. Of these, diphenyl carbonate is particularly preferred.

The (A) copolycarbonate may contain a structural unit derived from a dicarboxylic acid or a dicarboxylic acid ester, in addition to the above structural units. Examples of such dicarboxylic acid or dicarboxylic acid ester include the following compounds: terephthalic acid, isophthalic acid, sebacic acid, decanedioic acid, dodecanedioic acid, diphenyl sebacate, diphenyl terephthalate, diphenyl isophthalate. , Diphenyl decanedioate, diphenyl dodecanedioate, etc. When such a dicarboxylic acid or dicarboxylic acid ester is used in combination with a carbonic acid diester, a polyester polycarbonate is obtained. In the present invention, the above-mentioned dicarboxylic acid or dicarboxylic acid ester is used as carbonic acid diester 1
It can be contained in an amount of 50 mol or less, preferably 30 mol or less, relative to 00 mol.

The (A) copolycarbonate was prepared by using an Ubbelohde viscometer at 20 ° C. in methylene chloride (0.5 g /
The intrinsic viscosity [η] measured by dl) is preferably 0.2 to 1.2 dl / g, more preferably 0.3 to 0.8.
dl / g. If the intrinsic viscosity number is lower than the above range, the mechanical strength tends to decrease, and if it exceeds the above range, the moldability tends to decrease.

The (A) copolycarbonate usually has a yellowness index (YI) of 3 or less, which is measured as follows.
It is preferably 2.5 or less, and is less colored and excellent in hue.

That is, using a 3 mm thick pressed sheet of copolycarbonate as a sample, Colo manufactured by Nippon Denshoku Industries Co., Ltd.
Using the r and Defference Meter ND-1001 DP, measurement is performed by the transmission method, and the obtained X value, Y value and Z value are substituted into the following equation to calculate the YI value.

[0029]

## EQU1 ## YI = (100 / Y) × (1.277X−
1.060Z) (A) The copolycarbonate has a high melt elasticity and a high melt strength and is excellent in molding characteristics, and is more excellent in moldability than a polycarbonate not containing the structural unit represented by the above formula [II]. . Furthermore, it is excellent in hue and transparency.

The copolycarbonate (A) can be prepared, for example, by an interfacial polycondensation method using the aromatic dihydroxy compound represented by the general formula [III], the aromatic dihydroxy compound represented by the general formula [IV], and phosgene. It can be manufactured. However, it is preferably manufactured by the manufacturing method described below (method described in JP-A-7-149887). That is, the following formula [III]:

[0031]

[Chemical 7] (In the above formula, X, R ¹ , R ² , m and n are as defined above), an aromatic dihydroxy compound represented by the following formula [IV]:

[0032]

Embedded image (In the above formula, Y, R ⁶ , R ⁷ , R ⁸ , p and q have the same meanings as defined above),
And the carbonic acid diester is melt polycondensed in the presence of a catalyst (a) selected from alkali metal compounds and alkaline earth metal compounds.

In the above-mentioned method, as the aromatic dihydroxy compound represented by the general formula [III] and the aromatic dihydroxy compound represented by the general formula [IV], the compounds already concretely described above can be preferably used.

The aromatic dihydroxy compound represented by the general formula [IV] is contained in an amount of 8 × 10 ^{−5 to} 3 × 10 ⁻² mol per 1 mol of the aromatic dihydroxy compound represented by the general formula [III]. It is used in a proportion of preferably 2.5 × 10 ⁻⁴ to 1 × 10 ⁻² mol, more preferably 5 × 10 ^{−4 to} 5 × 10 ⁻³ mol.

Further, as the carbonic acid diester, the compounds already specifically described above can be preferably used. Of these, diphenyl carbonate is preferred.

In the above production method, the carbonic acid diester as described above is 1.0 to 1.30 mol, preferably 1. to 1.30 mol per 1 mol of the total amount of the aromatic dihydroxy compounds [III] and [IV]. It is desirable to use it in an amount of 01 to 1.20 mol, more preferably 1.01 to 1.10 mol.

In the above production method, the above-mentioned dicarboxylic acid or dicarboxylic acid ester may be used in an amount of 50 mol or less, preferably 30 mol or less, based on 100 mol of carbonic acid diester.

In the above production method, each of the above compounds is melt polycondensed in the presence of a catalyst (a) selected from an alkali metal compound and an alkaline earth metal compound.

Specific examples of such alkali metal compounds or alkaline earth metal compounds used as catalysts include organic acid salts, inorganic acid salts, oxides, hydroxides of alkali metals or alkaline earth metals, Preference is given to hydrides or alcoholates.

More specifically, such alkali metal compounds include sodium hydroxide, potassium hydroxide,
Lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride , Lithium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium Salts, dilithium salts, sodium salts of phenol, potassium salts, lithium salts and the like are used.

Specific examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate and carbonic acid. Calcium, barium carbonate,
Magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like are used.

These compounds can be used alone or in combination.

The catalyst (a) selected from the alkali metal compound and the alkaline earth metal compound is a total (total amount) of the aromatic dihydroxy compounds [III] and [IV].
It is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol, and more preferably 1 ×.
It is used in an amount of 10 ^{−7 to} 3 × 10 ⁻⁶ mol. (a) When a catalyst selected from an alkali metal compound and an alkaline earth metal compound is used in such an amount, the polymerization activity can be maintained high, and the hue, heat resistance, water resistance and weather resistance are excellent, and the time is long. A copolycarbonate having excellent melt stability can be obtained. Further, if the amount is such a level, the acidic compound ((a) of the component (C) described later) is an amount that does not adversely affect the properties of the obtained copolycarbonate.
Can be added to sufficiently neutralize or weaken the basicity of these compounds. In the above production method, in addition to (a), (b) a nitrogen-containing basic compound and / or (c) a boric acid compound can be used as a catalyst.

Examples of such a nitrogen-containing basic compound (b) include nitrogen-containing basic compounds which are easily decomposable or volatile at high temperature, and specifically, the following compounds are mentioned. Possible: Tetramethylammonium hydroxide (Me ₄ NOH, Me = methyl, the same below), Tetraethylammonium hydroxide (Et ₄ NOH, Et = ethyl, the same below), Tetrabutylammonium hydroxide (Bu ₄ NOH, Bu = Butyl) , The same below), trimethylbenzylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH, φ =
(Phenyl) and the like, ammonium hydroxides having alkyl, aryl, araryl groups, etc .; tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, trioctylamine, tridodecylamine, trioctadecylamine; R ₂ NH (in the formula, R is an alkyl group such as methyl or ethyl, or an aryl group such as phenyl or toluyl)
Secondary amines represented by RNH ₂ (wherein R is as defined above) primary amines; pyridines such as 4-dimethylaminopyridine, 4-diethylaminopyridine and 4-pyrrolidinopyridine; 2 -Imidazoles such as methyl imidazole, 2-phenyl imidazole and 2-dimethylamino imidazole; ammonia; tetramethyl ammonium borohydride (Me ₄ N BH ₄ ), tetrabutyl ammonium borohydride (Bu ₄ N BH ₄ ), tetra Butyl ammonium tetraphenylborate (Bu ₄ NBPh
₄ ), basic salts such as tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ ). Among these, tetraalkylammonium hydroxides, especially electron-use tetraalkylammonium hydroxides containing few metal impurities are preferably used.

(B) The nitrogen-containing basic compound is preferably 1 × 10 ^{-6 with} respect to 1 mol of the total amount of the aromatic dihydroxy compound.
It is used in an amount of ˜1 × 10 ⁻¹ mol, more preferably 1 × 10 ^{−5 -1} × 10 ⁻² mol. When (b) is used in such an amount, the transesterification reaction and the polymerization reaction proceed at a sufficient rate, and a copolycarbonate excellent in hue, heat resistance, water resistance and the like can be obtained, which is preferable.

A catalyst obtained by combining (a) a catalyst selected from an alkali metal compound and an alkaline earth metal compound with (b) a nitrogen-containing basic compound is excellent in heat resistance and water resistance and has an improved color tone. A high-molecular-weight copolycarbonate having excellent transparency can be produced with high polymerization activity.

Examples of the boric acid compound (c) include boric acid and boric acid ester. As the boric acid ester, a boric acid ester represented by the following general formula is used.

[0048]

Embedded image B (OR ′) _n (OH) _3-n (wherein R ′ is an alkyl group such as methyl or ethyl,
And aryl groups such as phenyl, and n is 1, 2 or 3. Examples of such boric acid ester include trimethyl borate, triethyl borate, tributyl borate,
Examples thereof include trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate. (c) The boric acid compound is preferably 1 × 10 ^-8 to 1 with respect to 1 mol of the total amount of the aromatic dihydroxy compound.
X10 ^-1 mol, more preferably 1 x 10 ^-7 to 1 x 10 ^-2 mol,
More preferably, it is used in an amount of 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol. (c) When boric acid or boric acid ester is used in such an amount, the molecular weight is less likely to decrease at high temperature, and a copolycarbonate excellent in hue, heat resistance and water resistance is obtained, which is preferable.

Particularly when (a) a catalyst selected from alkali metal compounds and alkaline earth metal compounds and (b) a large amount of nitrogen-containing basic compounds are used, (c) a boric acid compound is further added. The catalyst of the combination consisting of <3> has excellent transparency, heat resistance, water resistance and color tone, and is capable of producing a high molecular weight copolycarbonate with high polymerization activity.

The polycondensation reaction of the aromatic dihydroxy compound and the carbonic acid diester in the presence of a catalyst can be carried out under the same conditions as the conventionally known polycondensation reaction conditions of the aromatic dihydroxy compound and the carbonic acid diester. .

Specifically, the reaction in the first step is usually 80 to
Aromatic dihydroxy is performed at a temperature of 250 ° C., preferably 100 to 230 ° C., more preferably 120 to 190 ° C., usually 0 to 5 hours, preferably 0 to 4 hours, more preferably 0 to 3 hours under normal pressure. The compound is reacted with the carbonic acid diester. Then, the reaction temperature is raised while reducing the pressure of the reaction system to carry out the reaction between the aromatic dihydroxy compound and the carbonic acid diester, and finally, the aromatic dihydroxy compound is heated at a temperature of 240 to 320 ° C. under a reduced pressure of 5 mmHg or less, preferably 1 mmHg or less. A polycondensation reaction between the compound and carbonic acid diester is carried out.

The polycondensation reaction as described above may be carried out continuously or batchwise. The reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

According to the above production method, a uniform and stable branched polycarbonate can be obtained without formation of gel during polymerization, as compared with the interfacial polycondensation method using phosgene.

The above-mentioned method for producing copolycarbonate has an advantage that the copolycarbonate can be produced at a lower cost as compared with the interfacial method and that it is not necessary to use a substance such as phosgene which causes environmental pollution as a raw material. .

The (A) copolycarbonate has an alkali metal compound and / or alkaline earth metal compound content of 1 ppm or less and a chlorine content of 0.1 ppm or less,
The content of other metals is preferably 0.1 ppm or less.

Next, the component (B) in the composition of the present invention
As the filler, those generally known as fillers and reinforcing agents can be arbitrarily used. As such fillers and reinforcing agents, both inorganic compounds and organic compounds can be used. As the inorganic compound, powdery, as a plate-shaped inorganic compound, for example, silica, alumina, silica-alumina, talc, diatomaceous earth, clay, barium sulfate, calcium silicate, kaolin, quartz, glass, mica,
Examples thereof include graphite, molybdenum disulfide, gypsum, red iron oxide, titanium dioxide, zinc oxide, aluminum, copper and stainless steel. Further, as the fibrous inorganic compound, for example, glass fiber, carbon fiber, boron fiber,
Ceramic fibers, asbestos fibers, stainless steel fibers and the like can be mentioned, and secondary processed products such as cloth-like products can also be used. Examples of the organic compound include nylon, wholly aromatic polyamide such as aramid, polyamideimide, polyimide, polyester, polybenzimidazole, heterocyclic compound such as polyimidazophenanthroline, and polytetrafluoroethylene. These secondary processed products such as powdery, plate-like or fibrous products, or cloth products can be used. These fillers and reinforcing agents may be treated with a silane coupling agent, a titanium coupling agent, or the like. Particularly preferably, it is selected from powdery or plate-like glass, glass fiber and carbon fiber.

The blending amount of the (B) filler is determined according to the intended use of the composition. Preferably, 2 to 95 parts by weight of the (B) filler is blended with 98 to 5 parts by weight of (A). More preferably, 15 to 90 parts by weight of the (B) filler is blended with 85 to 10 parts by weight of (A). If the compounding amount of the filler is too large, the moldability of the resin composition will deteriorate, and if it is too small, the strength of the resin composition will decrease.

The resin composition of the present invention preferably further comprises (C) an additive. Such additives are:
(A) a sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound,
It is selected from the group consisting of (b) phosphorus compounds, (c) epoxy compounds, and (d) phenolic stabilizers.
These may be used alone or in combination of two or more, and may be added separately or simultaneously. The existence of (a), (b) and (d) above
It acts to neutralize or weaken the alkaline catalyst remaining in the above-mentioned (A) copolycarbonate. In addition, when (c) is present at the same time as (a) and (b), even if (a) and (b) are excessively present, they react with (c) and are neutralized, and The residence stability of the composition upon melting is further improved, and a composition with improved quality can be obtained, which is preferable.

(A) The sulfur-containing acidic compound having a pKa value of 3 or less and / or the derivative formed from the acidic compound include, for example, sulfurous acid, sulfuric acid, sulfinic acid compounds, sulfonic acid compounds and derivatives thereof. Can be mentioned.

Examples of the sulfite derivative include dimethyl sulfite, diethyl sulfite, dipropyl sulfite, dibutyl sulfite, diphenyl sulfite and the like.

Examples of the sulfuric acid derivative include dimethyl sulfuric acid, diethyl sulfuric acid, dipropyl sulfuric acid, dibutyl sulfuric acid and diphenyl sulfuric acid.

Examples of the sulfinic acid compound include benzenesulfinic acid, toluenesulfinic acid and naphthalene sulphinic acid.

As the sulfonic acid compound, the following formula (i)

[0064]

Embedded image [Here, R ^a is a hydrocarbon group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a halogen atom), and R ^b
Is a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a halogen atom), and n is an integer of 0 to 3] and an ammonium salt thereof. Can be mentioned. Specifically, for example, sulfonic acids such as benzene sulfonic acid and p-toluene sulfonic acid; methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfonic acid. Sulfonic acid esters such as methyl, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; ammonium sulfonate such as ammonium p-toluenesulfonate, etc. To be In addition to the compound represented by the above formula (i), trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene, methyl acrylate-sulfonated styrene copolymer, anhydride of sulfonic acids, anhydride of sulfonic acids and carboxylic acids A compound such as a substance can also be used.

These compounds can be used alone or in combination.

As the sulfur-containing acidic compound having a pKa value of 3 or less and / or the derivative formed from the acidic compound, the sulfonic acid compound represented by the above formula (i) is preferably used. Further, in the above formula (i), a compound in which R ^a and R ^b are both substituted aliphatic hydrocarbon groups having 1 to 10 carbon atoms and n is an integer of 0 to 1 is preferable. Specifically, benzene sulfonic acid, butyl benzene sulfonate, p-toluene sulfonic acid, ethyl p-toluene sulfonate and butyl p-toluene sulfonate are preferable. Particularly preferred is butyl p-toluenesulfonate.

(A) The sulfur-containing acidic compound having a pKa value of 3 or less and / or the derivative formed from the acidic compound is preferably 0.1 to 10 ppm, more preferably more preferably 0.1 to 10 ppm, based on the above-mentioned (A) copolycarbonate. Is 0.1 to 8
ppm, particularly preferably 0.1-5 ppm.

The composition of the present invention has the above-mentioned (a) pKa.
When the sulfur-containing acidic compound having a value of 3 or less and / or the derivative formed from the acidic compound is contained, the copolycarbonate (A) may further contain 5-1000 ppm of water. By adding water in such an amount, the neutralization efficiency of the acidic compound with respect to the catalyst is increased, and thermal stability at the time of melting, retention stability such as hue stability and hue, transparency, water resistance, and weather resistance are improved. Further improve.

Next, as the (b) phosphorus compound, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid,
Phosphate esters and phosphite esters are preferably used. Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, tris (2-chloroethyl) phosphate, tris (2,3-). Trialkyl phosphates such as dichloropropyl) phosphate; tricycloalkyl phosphates such as tricyclohexyl phosphate; triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate, etc. To be

Examples of the phosphite ester include compounds represented by the following general formula (ii).

[0071]

Embedded image P (OR ^c ) ₃ (ii) (In the above formula, R ^c represents an alicyclic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, which may be the same or different. Specifically, for example, trimethylphosphite, triethylphosphite, tributylphosphite, trioctylphosphite, tris (2-ethylhexyl) phosphite, trinonylphosphite, tridecylphosphite, trioctadecylphosphite. Fight, tristearyl phosphite, tris (2-chloroethyl) phosphite,
Trialkyl phosphites such as tris (2,3-dichloropropyl) phosphite; tricycloalkyl phosphites such as tricyclohexyl phosphite; triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (2,4-di-t-
Butylphenyl) phosphite, tris (nonylphenyl) phosphite, triarylphosphite such as tris (hydroxyphenyl) phosphite; phenyldidecylphosphite, diphenyldecylphosphite,
Examples thereof include arylalkyl phosphites such as diphenylisooctylphosphite, phenyldiisooctylphosphite, and 2-ethylhexyldiphenylphosphite.

Further, as the phosphite, distearyl pentaerythrityl diphosphite, bis (2,4-
It is also possible to use di-t-butylphenyl) pentaerythrityl diphosphite.

These compounds can be used alone or in combination.

The (b) phosphorus compound is preferably a phosphite represented by the above general formula (ii), more preferably an aromatic phosphite, and particularly preferably tris (2,4-di-t). -Butylphenyl) phosphite.

The (b) phosphorus compound is preferably added in an amount of 10 to 1000 ppm, more preferably 50 to 500 ppm, relative to the above-mentioned (A) copolycarbonate.

Next, as the (c) epoxy compound, 1
A compound having one or more epoxy groups in the molecule is used. Specifically, epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 3 , 4-Epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3', 4'-epoxycyclohexylcarboxylate, 4- (3 , 4-Epoxy-5-methylcyclohexyl) butyl-3 ', 4'-epoxycyclohexylcarboxylate,
3,4-epoxycyclohexyl ethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl
-6'-methylcyclohexylcarboxylate, bisphenol-A diglycidyl ether, tetrabromobisphenol-A glycidyl ether, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, bis-epoxydicyclopentadienyl ether,
Bis-epoxy ethylene glycol, bis-epoxy cyclohexyl adipate, butadiene diepoxide, tetraphenyl ethylene epoxide, octyl epoxytalate, epoxidized polybutadiene, 3,4-dimethyl-1,2
-Epoxycyclohexane, 3,5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-
Epoxy cyclohexyl carboxylate, N-butyl-
2,2-Dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate , Octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-
Epoxy cyclohexyl-3 ', 4'-epoxy cyclohexyl carboxylate, 4,5-epoxy tetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxy tetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis -1 , 2-Cyclohexyldicarboxylate, di-n-butyl-3-t-butyl
Examples include -4,5-epoxy-cis-1,2-cyclohexyldicarboxylate. Of these, alicyclic epoxy compounds are preferable, and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate is particularly preferable.

These compounds can be used alone or in combination.

(C) The epoxy compound is the above-mentioned (A).
For copolycarbonates, preferably 1 to 2000 pp
m, more preferably 10 to 1000 ppm.

Next, (d) phenolic stabilizers include, for example, n-octadecyl-3- (4-hydroxy-3 ', 5'-di-
-t-Butylphenyl) propionate, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl)
-4-Hydroxy-5-t-butylphenyl) butane, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzyl malonate, 4-hydroxymethyl-2,6-di-t-butylphenol, etc. And even if these are used alone, 2
You may mix and use more than one kind.

The (d) phenolic stabilizer is preferably 10 to 10 relative to the above-mentioned (A) copolycarbonate.
It is added in an amount of 00 ppm, more preferably 50 to 500 ppm.

In producing the composition of the present invention, the respective components can be mixed by a conventionally known method. For example, after each component is dispersed and mixed in a high speed mixer represented by a turnbull mixer or a Henschel mixer, an extruder,
A method of melt-kneading with a Banbury mixer, a roll or the like is appropriately selected.

Particularly preferred is a method in which the (A) copolycarbonate in the molten state after the completion of the polycondensation reaction is directly added with the (B) filler or preferably with the (C) additive and kneading. The addition may be carried out while the (A) copolycarbonate is in the final polymerization vessel, or may be carried out in the molten state while being introduced into the extruder from the reactor. This method is preferable because it is possible to reduce the heat history applied to the resin and to obtain a copolycarbonate composition that is excellent in retention stability with less deterioration in hue and heat. In addition, a product with stable quality can be obtained at low cost.

The composition produced is usually then pelletized. Pelletization can be performed by passing the composition through an extruder.

The pelletized composition is re-melted at the time of use, and various additives can be blended as necessary for use. The composition produced by the above-described preferred method has good thermal stability when melted, so that even if it is remelted when blending or molding various additives, thermal decomposition is particularly suppressed and the molecular weight is unlikely to decrease. Moreover, even if it melts, it is hard to discolor.

When the composition of the present invention contains the additive (C), the order of adding (B) and (C) to (A) does not matter.

The composition of the present invention is a heat-resistant stabilizer (excluding phenol-based stabilizers, organic phosphorus-based stabilizers and epoxy-based stabilizers), an ultraviolet absorber, and a release agent within the range that does not impair the object of the present invention. Conventional additives such as colorants, antistatic agents, slip agents, antiblocking agents, antifog agents, lubricants, natural oils, synthetic oils, waxes, flame retardants and the like. Such an additive can be added to (A) in a molten state at the same time as the above-mentioned (C) additive,
It can also be added when remelting the pellets of the composition of the present invention once produced. In the present invention, the former is preferable.

Next, regarding some of the above-mentioned additives,
Describe in detail. First, examples of the heat resistance stabilizer include organic thioether-based stabilizers and hindered amine-based stabilizers.

Examples of the thioether stabilizers include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, Pentaerythritol-tetrakis- (β-lauryl-thiopropionate) and the like can be mentioned.

Examples of the hindered amine stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl).
Sebacate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3-
(3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl -1,2,3-Triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2- (3,
5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6-) And tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate.

These may be used alone or in combination. These heat stabilizers may be added in a solid state,
You may add in liquid form. The heat resistance stabilizer is added when (A) is in a melted state, that is, when (A) is in a melted state between the time when it is produced and the time when it is sent to the extruder from the final polymerization vessel and pelletized. Preferably. By doing so, the number of thermal histories received by the (A) copolycarbonate is small. Further, if added in this way, thermal decomposition can be suppressed when heat treatment is again performed such as extrusion molding or pelletization.

The heat resistance stabilizer is (A) copolycarbonate.
It is generally used in an amount of 0.001 to 5 parts by weight, preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight.

As the ultraviolet absorber, a general ultraviolet absorber can be used and is not particularly limited. For example, salicylic acid type ultraviolet absorber, benzophenone type ultraviolet absorber, benzotriazole type ultraviolet absorber, cyanoacrylate type ultraviolet absorber. An agent etc. can be mentioned.

Specific examples of the salicylic acid type ultraviolet absorber include phenyl salicylate and pt-butylphenyl salicylate.

As the benzophenone type ultraviolet absorber,
Specifically, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy
-4-methoxybenzophenone, 2,2'-dihydroxy-4,4 '
-Dimethoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2,2 ' , 4,4'-
Tetrahydroxybenzophenone, 4-dodecyloxy-2-
Hydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy
-4-Methoxybenzophenone-5-sulfonic acid and the like can be mentioned.

Specific examples of the benzotriazole type ultraviolet absorber include 2- (2'-hydroxy-5'-methyl-phenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-.
Di-t-butyl-phenyl) benzotriazole, 2- (2 '
-Hydroxy-3'-t-butyl-5'-methyl-phenyl) -5-
Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-t-butyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di -t-
Amylphenyl) benzotriazole, 2- [2'-hydroxy -3 '-(3'',4'',5'',6''-tetrahydrophthalimidomethyl)-5'-methylphenyl] benzotriazole,
2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like can be mentioned.

Examples of the cyanoacrylate ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate and ethyl-2-cyano-3,3-diphenyl acrylate.

These may be used alone or in combination.

The ultraviolet absorber is usually 0.001 to 5 parts by weight, preferably 0.005 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight, relative to 100 parts by weight of the (A) copolycarbonate.
Used in parts by weight.

As the release agent, a general release agent can be used and is not particularly limited. For example, hydrocarbon-based release agents; fatty acid-based release agents; fatty acid amide-based release agents; alcohol-based release agents; fatty acid ester-based release agents; silicone-based release agents and the like.

Examples of the hydrocarbon releasing agent include natural releasing agents,
Examples include synthetic paraffins, polyethylene waxes, fluorocarbons and the like.

Examples of the fatty acid-based release agent include higher fatty acids such as stearic acid and hydroxystearic acid, and oxyfatty acids.

Examples of the fatty acid amide type release agent include stearic acid amides, fatty acid amides such as ethylene bis stearoamide, and alkylene bis fatty acid amides.

Examples of the alcohol-based releasing agent include aliphatic alcohols such as stearyl alcohol and cetyl alcohol, polyhydric alcohols, polyglycols and polyglycerols.

Examples of the fatty acid ester-based releasing agent include lower fatty acid esters of aliphatic acids such as butyl stearate and pentaerythritol tetrastearate, fatty acid polyhydric alcohol esters, and fatty acid polyglycol esters.

Examples of the silicone type release agent include silicone oils. These may be used alone or in combination.

The releasing agent is (A) copolycarbonate 100.
Usually, 0.001 to 5 parts by weight, preferably 0.
It is used in an amount of 005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight.

The colorant may be a pigment or a dye, and may be an inorganic type or an organic type. Further, these may be used in combination.

Specific examples of the inorganic colorant include oxides such as titanium dioxide and red iron oxide, hydroxides such as alumina white, sulfides such as zinc sulfide, selenides, ferrocyanides such as navy blue, and zinc chromate. , Chromate such as molybdenum red, sulfate such as barium sulfate, carbonate such as calcium carbonate, silicate such as ultramarine blue,
Examples thereof include phosphates such as manganese violet, carbon such as carbon black, and metal powder colorants such as bronze powder and aluminum powder.

Specific examples of the organic colorant include nitroso type such as naphthol green B, nitro type such as naphthol yellow S, resole red and bordeaux 10.
Examples thereof include azo colorants such as B, naphthol red, and chromophthal yellow, phthalocyanine colorants such as phthalocyanine blue and fast sky blue, condensed polycyclic colorants such as indanthrone blue, quinacridone violet, and dioxazine violet.

These colorants may be used alone or in combination.

These colorants are usually used in an amount of 1 × 10 ^{−6 to} 5 parts by weight, preferably 1 × 10 ^{−5 to} 3 parts by weight, and more preferably 1 × 10 ⁵ parts by weight, based on 100 parts by weight of the (A) copolycarbonate.
Used in an amount of ^-5 to 1 part by weight.

The composition of the present invention is superior in moldability to a composition containing a usual bisphenol-based homopolycarbonate, is less likely to undergo thermal decomposition during molding, is less likely to have a reduced molecular weight, and is less likely to be yellowed, It also has excellent hue stability and can form a molded article having excellent hue stability for a long time even when used.

The composition of the present invention is particularly useful as a composition for blow molding and injection molding. The composition of the present invention comprises:
It can be used in a wide range of applications such as automobile applications, electric parts, communication device parts, precision instruments, and optical applications.

[0114]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

The composition and physical properties of the copolycarbonates and their compositions obtained in the following synthesis examples and examples were measured as follows, and the moldability and appearance were evaluated. 1) Analysis of constitutional unit of copolycarbonate The constitutional unit derived from the aromatic dihydroxy compound in the resin and the ratio thereof were examined by measuring ¹³ C-NMR. The measurement conditions of ¹³ C-NMR were as follows: Measuring device: ¹³ C-NMR GX-270 (manufactured by JEOL Ltd.) Measuring solvent: CDCl ₃ Standard substance: CDCl ₃ (77.00 ppm) Sample preparation Method: 0.4 g of polymer was dissolved in ₃ ml of CDCl ₃ .

Measurement conditions: 110 MHz, accumulated 30,000 times 2) Intrinsic viscosity [η] It was measured in methylene chloride (0.5 g / dl) at 20 ° C. using an Ubbelohde viscometer. 3) Yellowness [YI] 3mm thick press sheet is manufactured by Nippon Denshoku Industries Co., Ltd.
The X value, Y value, and Z value measured by the transmission method using Color and DefferenceMeter ND-1001 DP were substituted into the following formula to calculate.

[0117]

(2) YI = (100 / Y) × (1.277X−
1.060Z) 4) Light transmittance A press sheet with a thickness of 3 mm is manufactured by Nippon Denshoku Industries Co., Ltd.
It measured using NDH-200. 5) Haze 3 mm thick press sheet from Nippon Denshoku Industries Co., Ltd.
It measured using NDH-200. 6) Melt flow rate (MFR) According to the method of JIS K-7210, temperature 300 ° C,
The load was measured at 1.2 kg. 7) Blow Moldability After the molten resin was fed to the mold by the extruder, the bottle was blow molded and the ease of molding (moldability) was examined. Molding conditions are as follows: cylinder temperature 250 ℃, mold temperature 80
℃, blowing air pressure 5kgf / cm ² , total cycle 12 seconds. 8) Injection moldability Ease of molding by molding a 3 mm thick injection molded plate (moldability)
Was examined. Molding conditions are as follows: Cylinder temperature 280
℃, mold temperature 80 ℃, total cycle 12 seconds. 9) Appearance The appearance (hue and surface glossiness) of the injection molded plate of 8) was examined.

Synthesis Example 1 Monocarboxylated bisphenol A [ie 2- (4-hydroxy) was obtained by carboxylating bisphenol A potassium salt with carbon dioxide gas and recrystallizing with a toluene solvent for purification. Phenyl) -2-
(3'-Carboxy-4'-hydroxyphenyl) propane]
I got This monocarboxylated bisphenol A was esterified with a large excess of diphenyl carbonate and then purified by column purification to a purity of 99% or more (HPLC
By analysis) 2- (4-hydroxyphenyl) -2- (3'-
Phenoxycarbonyl-4'-hydroxyphenyl) propane was obtained.

Bisphenol A (manufactured by Japan GE Plastics Co., Ltd.) 0.44 kmole, prepared as described above 2-
1.3 mol of (4-hydroxyphenyl) -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) propane and 0.46 kmole of diphenyl carbonate (manufactured by Any Co.) were charged in a 250 liter tank-type stirring tank, and nitrogen was added. After replacement, the solution was melted at 140 ° C.

Next, this was heated to a temperature of 180 ° C., and tetramethylammonium hydroxide as a catalyst was added to 0.2%.
11 mol and 0.00044 mol of sodium hydroxide (1 × 10 ⁻⁶ mol / mol-bisphenol A) were added to 30
Stir for minutes.

Next, the temperature was raised to 210 ° C. and, at the same time, gradually lowered to 200 mmHg and 30 minutes later, the temperature was raised to 2
The temperature was raised to 40 ° C. and, at the same time, gradually lowered to 15 mmHg, the temperature and pressure were kept constant, and the amount of phenol to be distilled out was measured. When the phenol to be distilled out was exhausted, the pressure was returned to atmospheric pressure with nitrogen. The time required for the reaction was 1 hour.
The intrinsic viscosity [η] of the obtained reaction product was 0.15 dl /
g.

Next, the pressure of this reaction product was increased by a gear pump, and the reaction product was fed into a centrifugal thin-film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. From the bottom of the evaporator with a gear pump at 290 ℃, 0.
Biaxial horizontal stirring polymerization tank controlled to 2 mmHg (L
/ D = 3, stirring blade rotating diameter 220 mm, internal volume 80 liters) was fed at 40 kg / hour and polymerized for a residence time of 30 minutes.

¹³ C-NMR of the polymer thus obtained
From the measurement results, this polymer is a copolycarbonate having a constitutional unit represented by the following formulas [V] and [VI] as a component derived from an aromatic dihydroxy compound in a molar ratio of 99.7: 0.3. It was confirmed.

[0124]

[Chemical 12]

[0125]

Embedded image ^{The 13} C-NMR chart is shown in FIGS. 1 and 2, and the attribution of each peak is shown in FIG. The peaks derived from the carbon atoms at the positions of and were observed at 123.07 ppm and 162.91 ppm, respectively.

The copolycarbonate thus obtained was treated with C
It is called PC-1. The intrinsic viscosity [η] of this copolycarbonate was 0.49 dl / g. Table 1 for each physical property
Shown in

Synthesis Example 2 In Synthesis Example 1, bisphenol A and 2- (4-hydroxyphenyl) -2- (3'-phenoxycarbonyl-4'-
The molar ratio of (hydroxyphenyl) propane charged was 9
A copolycarbonate was produced in the same manner as in Synthesis Example 1 except that the ratio was changed from 9.8 to 0.2.

¹³ C-NMR of the polymer thus obtained
From the measurement results, this polymer is a copolycarbonate having the constituent units represented by the above formulas [V] and [VI] as a component derived from an aromatic dihydroxy compound in a molar ratio of 99.8: 0.2. I understand. That is, as a result of ¹³ C-NMR analysis, the and peaks (123.07 ppm and 162.91 ppm) in the ¹³ C-NMR chart of the polymer produced in Synthesis Example 1 were obtained.
) Was 2/3 of the peak intensity of Synthesis Example 1.

The copolycarbonate thus obtained was treated with C
It is called PC-2. The intrinsic viscosity [η] of this copolycarbonate was 0.49 dl / g. Table 1 for each physical property
Shown in

Synthesis Example 3 In Synthesis Example 1, bisphenol A and 2- (4-hydroxyphenyl) -2- (3'-phenoxycarbonyl-4'-
The charged molar ratio of (hydroxyphenyl) propane was 99.
A copolycarbonate was produced in the same manner as in Synthesis Example 1 except that 9: 0.1 was used.

¹³ C-NMR of the polymer thus obtained
From the measurement results, this polymer is a copolycarbonate having the structural units represented by the above formulas [V] and [VI] as a component derived from an aromatic dihydroxy compound in a molar ratio of 99.9 to 0.1. I understand. That is, as a result of ¹³ C-NMR analysis, the and peaks (123.07 ppm and 162.91 ppm) in the ¹³ C-NMR chart of the polymer produced in Synthesis Example 1 were obtained.
) Was 1/3 of the peak intensity of Synthesis Example 1.

The copolycarbonate thus obtained was treated with C
It is called PC-3. The intrinsic viscosity [η] of this copolycarbonate was 0.49 dl / g. Table 1 for each physical property
Shown in

Synthesis Example 4 A polycarbonate was produced in the same manner as in Synthesis Example 1 except that 2- (4-hydroxyphenyl) -2- (3'-phenoxycarbonyl-4'-hydroxyphenyl) propane was not used. .

¹³ C-NMR of the polymer thus obtained
From the measurement results, it was found that this polymer was a polycarbonate having only a unit derived from bisphenol A as a component derived from an aromatic dihydroxy compound. That, ¹³ C-NMR results of the analysis of, ¹³ C-NMR and the chart of the peaks of the polymer prepared in Synthesis Example 1 (123.07ppm and 16
2.91 ppm) was not recognized.

This polycarbonate is called PC. The intrinsic viscosity [η] was 0.49 dl / g. Table 1 shows each physical property value.

[0136]

[Table 1] * 1 Molar ratio of structural units [V] and [VI] ([V] / [VI]) Example 1 Copolycarbonate (CPC) produced in Synthesis Example 1
-1) was used to produce a composition as follows.

That is, the CPC-1 in the molten state was converted into an aromatic dihydroxy compound every hour by a gear pump in a twin-screw extruder (L / D = 17.5, barrel temperature 285 ° C.).
0.16 kmole (approx. 40 kg / hour) was fed into each, and 70 parts by weight of glass fiber (chip strand CS6PE-231: Nitto Boseki Co., Ltd.) having an average length of 6 mm and copolycarbonate per 100 parts by weight of copolycarbonate. On the other hand, 1.8 ppm of butyl p-toluenesulfonate and 5 parts of distilled water
0 ppm, tris (2,4-di-t-butylphenyl) phosphite (Mark 2112: manufactured by ADEKA ARGUS CORPORATION) 300 ppm,
n-Octadecyl-3- (4-hydroxy-3 ', 5',-di-t-butylphenyl) propionate (Mark AO50: ADEKA ARGAS Co., Ltd.) 300 ppm, and 3,4-epoxycyclohexyl Methyl-3 ', 4'-epoxycyclohexylcarboxylate (Celoxide 2021P: manufactured by Daicel Chemical Industries) 300
ppm was continuously kneaded, passed through a die to form a strand, and cut with a cutter to obtain pellets.

Injection molding and blow molding were carried out using the obtained pellets to evaluate the moldability, and the appearance of the obtained injection molded product was observed. Table 2 shows the results.

Example 2 Instead of CPC-1, CPC-2 prepared in Synthesis Example 2 was used.
A composition was prepared and pelletized in the same manner as in Example 1 except that was used. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. Table 2 shows the results.

Example 3 Instead of CPC-1, CPC-3 prepared in Synthesis Example 3 was used.
A composition was prepared and pelletized in the same manner as in Example 1 except that was used. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. Table 2 shows the results.

Comparative Example 1 A composition was prepared and pelletized in the same manner as in Example 1 except that the PC prepared in Synthesis Example 4 was used instead of CPC-1. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. Table 2 shows the results.

[0142]

[Table 2] * 1 Inferior in surface gloss and smoothness to Examples 1 to 3. * 2 Cannot be molded due to drawdown * 3 Surface gloss and smoothness are inferior to those of Examples 1-3. Example 4 A composition was prepared and pelletized in the same manner as in Example 1 except that the amount of glass fiber was changed from 70 parts by weight to 50 parts by weight. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. The results are shown in Table 3.

Example 5 CPC-3 prepared in Synthesis Example 3 instead of CPC-1
A composition was prepared and pelletized in the same manner as in Example 4 except that was used. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. The results are shown in Table 3.

Comparative Example 2 A composition was prepared and pelletized in the same manner as in Example 4 except that PC prepared in Synthesis Example 4 was used instead of CPC-1. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. The results are shown in Table 3.

[0145]

[Table 3] * 1 Cannot be molded due to drawdown * 2 Inferior in surface gloss and smoothness to Examples 4-5. Example 6 A composition was prepared and pelletized in the same manner as in Example 1 except that the amount of glass fiber was changed from 70 parts by weight to 40 parts by weight. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. The results are shown in Table 4.

Example 7 CPC-3 prepared in Synthesis Example 3 instead of CPC-1
A composition was prepared and pelletized in the same manner as in Example 6 except that was used. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. The results are shown in Table 4.

Comparative Example 3 A composition was prepared and pelletized in the same manner as in Example 6 except that the PC prepared in Synthesis Example 4 was used instead of CPC-1. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. The results are shown in Table 4.

[0148]

[Table 4] * 1 Cannot be molded due to drawdown * 2 Surface gloss and smoothness are inferior to Examples 6-7. Example 8 A composition was prepared and pelletized in the same manner as in Example 1 except that the amount of glass fiber was changed from 70 parts by weight to 20 parts by weight. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. Table 5 shows the results.

Example 9 CPC-3 prepared in Synthesis Example 3 instead of CPC-1
A composition was prepared and pelletized in the same manner as in Example 8 except that was used. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. Table 5 shows the results.

Comparative Example 4 A composition was prepared and pelletized in the same manner as in Example 8 except that PC prepared in Synthesis Example 4 was used instead of CPC-1. Injection molding and blow molding were performed using the obtained pellets in the same manner as in Example 1, and the appearance of the obtained injection molded product was observed. Table 5 shows the results.

[0151]

[Table 5] * 1 Cannot be molded due to drawdown * 2 Inferior in surface gloss and smoothness to Example 8.

[0152]

The composition of the present invention is excellent in moldability such as melt elasticity and melt strength in comparison with the conventional composition of bisphenol homopolycarbonate and filler. Therefore, it is very useful especially as a molding material for blow molding and injection molding. Further, the molded product obtained from the composition of the present invention is stable in hue over a long period of time and has excellent surface properties such as surface gloss. Moreover, mechanical characteristics such as rigidity,
It also has excellent heat resistance, water resistance, and transparency.

[Brief description of drawings]

FIG. 1 ¹³ C of copolycarbonate produced in Synthesis Example 1
-A chart showing the results of NMR analysis, 105-1
The range of 40 ppm is shown.

FIG. 2 is ¹³ C of the copolycarbonate produced in Synthesis Example 1.
-A chart showing the results of NMR analysis, 140-1
The range of 70 ppm is shown.

FIG. 3 ¹³ C of the copolycarbonate produced in Synthesis Example 1
-The attribution of each peak in the chart showing the result of NMR analysis is shown.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 7/06 C08K 7/06 7/14 KKN 7/14 KKN

Claims (8)

[Claims] 1. A copolycarbonate obtained by copolymerizing (A) two or more kinds of aromatic dihydroxy compounds and a compound capable of introducing a carbonic acid bond, which is a component unit derived from an aromatic dihydroxy compound. , The following formula [I]: (In the formula, X is ^{- (R 3 -) C (} -R 4) -, - C
^{(= R 5) -, -} O -, - S -, - SO- or -SO
_2- {wherein R ³ and R ⁴ are a hydrogen atom or a monovalent hydrocarbon group optionally substituted with halogen, and R ⁵
Is a divalent hydrocarbon group that may be substituted with halogen}, and R ¹ and R ² may be the same or different, and the number of carbon atoms that may be substituted with halogen, respectively. A hydrocarbon unit of 1 to 10 or a halogen atom, m and n represent the number of substituents, each independently an integer of 0 to 4), and a unit represented by the following formula [II]: ] (In the above formula, Y is-(R3 ^' -) C (-R4 ^' )-, -C
(= R5 ^' )-, -O-, -S-, -SO- or -SO
_2- {wherein R ^{3 '} and R ^4' are a hydrogen atom or a monovalent hydrocarbon group optionally substituted with halogen, and R ^{5 '}
Is a divalent hydrocarbon group which may be substituted with halogen}, and R ⁷ and R ⁸ may be the same or different and each has the number of carbon atoms which may be substituted with halogen. 1 to 10 hydrocarbon groups or halogen atoms, p and q represent the number of substituents, p is an integer of 0 to 4, and q is an integer of 0 to 3). A copolycarbonate composition comprising a copolycarbonate and (B) a filler. 2. The composition according to claim 1, wherein 2 to 95 parts by weight of the filler (B) is blended with 98 to 5 parts by weight of the (A) copolycarbonate. 3. The copolycarbonate (A) is a copolycarbonate obtained by copolymerizing two or more kinds of aromatic dihydroxy compounds and a compound capable of introducing a carbonic acid bond, and (1) the aromatic dihydroxy compound. As a component unit derived from, a structural unit represented by the above formula [I],
The constitutional unit represented by the formula [II] is in a ratio of 8 × 10 ^{−5 to} 3 × 10 ⁻² mols of the constitutional unit represented by [II] with respect to 1 mol of the constitutional unit represented by [I]. are contained (wherein, in the formula [I], X is ^{- (R 3 -) C (} -R 4)
^{-, - C (= R 5} ) -, - O -, - S -, - SO- or -SO ₂ - {wherein R ³ and R ⁴ are hydrogen atom or carbon atoms, which is substituted by halogen 1 to 15 linear, branched or cyclic monovalent hydrocarbon group,
R ⁵ has 1 to 15 carbon atoms which may be substituted with halogen.
Is a linear, branched or cyclic divalent hydrocarbon group}, and R ¹ and R ² may be the same or different and each may be a carbon atom which may be substituted with halogen. the number 1 to 10 linear, a hydrocarbon group or a halogen atom branched or cyclic, m and n are as defined above, also in the above formula [II], Y is - (R 3 ^'-) C
(-R4 ^' )-, -C (= R5 ^' )-, -O-, -S-,-
SO— or —SO ₂ — {wherein R ^{3 ′} and R ^{4 ′} have 1 carbon atoms which may be substituted with hydrogen atom or halogen.
Is a linear, branched or cyclic monovalent hydrocarbon group having 15 to 15 carbon atoms, and R ^{5 ′} is a linear, branched or cyclic divalent group having 1 to 15 carbon atoms which may be substituted with halogen. R ⁷ and R ⁸ may be the same or different and each may be linear or branched, having 1 to 10 carbon atoms, which may be substituted with halogen. A cyclic hydrocarbon group or a halogen atom, p and q are as defined above, and (2) in methylene chloride, 2
The intrinsic viscosity [η] measured at 0 ° C is 0.2 to 1.2 dl
A composition according to claim 1 or 2 which is a copolycarbonate wherein 4. The copolycarbonate (A), wherein in the formula [I], X is a linear or branched alkylene, and in the formula [II], Y is a linear or branched alkylene. A composition according to any one of claims 1 to 3, which is a copolycarbonate. 5. The (A) copolycarbonate having an alkali metal compound and / or alkaline earth metal compound content of 1 ppm or less, a chlorine content of 0.1 ppm or less, and other metal contents of 0.1 ppm or less. The composition according to any one of claims 1 to 4, which is a copolycarbonate. 6. The composition according to claim 1, wherein the filler (B) is selected from powdery or plate-like glass, glass fiber and carbon fiber. 7. (C) (a) Sulfur-containing acidic compound having a pKa value of 3 or less and / or a derivative formed from the acidic compound, (b) phosphorus compound, (c) epoxy compound, and ( D) It contains one or more additives selected from the group consisting of phenolic stabilizers.
The composition according to any one of claims 6 to 10. 8. The composition according to claim 1, which is a composition for blow molding or injection molding.